Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide

ABSTRACT

Methods and systems for heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide are disclosed. A method may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte, a heterocyclic catalyst, and a cathode. Step (C) may introduce a second reactant to the second compartment of the electrochemical cell. Step (D) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient to induce liquid phase carbonylation or hydroformylation to form a product mixture.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit under 35 U.S.C. §119(e) ofthe following applications:

U.S. Patent Application Ser. No. 61/417,956, entitled “HeterocycleCatalyzed Carbonylation with Carbon Dioxide,” filed Nov. 30, 2010.

U.S. Patent Application Ser. No. 61/418,054, entitled “HeterocycleCatalyzed Hydroformylation with Carbon Dioxide,” filed Nov. 30, 2010.

Each of the above-listed applications is hereby incorporated byreference in their entireties.

FIELD

The present disclosure generally relates to the field of electrochemicalreactions, and more particularly to methods and/or systems forheterocycle catalyzed carbonylation and hydroformylation with carbondioxide.

BACKGROUND

The combustion of fossil fuels in activities such as electricitygeneration, transportation, and manufacturing produces billions of tonsof carbon dioxide annually. Research since the 1970s indicatesincreasing concentrations of carbon dioxide in the atmosphere may beresponsible for altering the Earth's climate, changing the pH of theocean and other potentially damaging effects. Countries around theworld, including the United States, are seeking ways to mitigateemissions of carbon dioxide.

A mechanism for mitigating emissions is to convert carbon dioxide intoeconomically valuable materials such as fuels and industrial chemicals.If the carbon dioxide is converted using energy from renewable sources,both mitigation of carbon dioxide emissions and conversion of renewableenergy into a chemical form that can be stored for later use will bepossible.

However, the field of electrochemical techniques attempting to utilizecarbon dioxide as a reactant to form chemical products has manylimitations, including the stability of systems used in the process, theefficiency of systems, the selectivity of the systems or processes for adesired chemical, the cost of materials used in systems/processes, theability to control the processes effectively, and the rate at whichcarbon dioxide is converted. In particular, existing electrochemical andphotochemical processes/systems have one or more of the followingproblems that prevent commercialization on a large scale. Severalprocesses utilize metals, such as ruthenium or gold, that are rare andexpensive. In other processes, organic solvents were used that madescaling the process difficult because of the costs and availability ofthe solvents, such as dimethyl sulfoxide, acetonitrile, and propylenecarbonate. Copper, silver and gold have been found to reduce carbondioxide to various products, however, the electrodes are quickly“poisoned” by undesirable reactions on the electrode and often cease towork in less than an hour. Similarly, gallium-based semiconductorsreduce carbon dioxide, but rapidly dissolve in water. Many cathodesproduce a mixture of organic products. For instance, copper produces amixture of gases and liquids including carbon monoxide, methane, formicacid, ethylene, and ethanol. Such mixtures of products make extractionand purification of the products costly and can result in undesirablewaste products that must be disposed. Much of the work done to date oncarbon dioxide reduction is inefficient because of high electricalpotentials utilized, low faradaic yields of desired products, and/orhigh pressure operation. The energy consumed for reducing carbon dioxidethus becomes prohibitive. Many conventional carbon dioxide reductiontechniques have very low rates of reaction. For example, in order toprovide economic feasibility, a commercial system currently may requiredensities in excess of 100 milliamperes per centimeter squared (mA/cm²),while rates achieved in the laboratory are orders of magnitude less.

SUMMARY

A method for mitigation of carbon dioxide through heterocycle catalyzedhydroformylation using carbon dioxide may include, but is not limitedto, steps (A) to (D). Step (A) may introduce water to a firstcompartment of an electrochemical cell. The first compartment mayinclude an anode. Step (B) may introduce carbon dioxide to a secondcompartment of the electrochemical cell. The second compartment mayinclude a solution of an electrolyte, a heterocyclic catalyst, and acathode. Step (C) may introduce an alkene to the second compartment ofthe electrochemical cell. Step (D) may apply an electrical potentialbetween the anode and the cathode in the electrochemical cell sufficientto induce liquid phase hydroformylation to form a product mixture.

A method for mitigation of carbon dioxide through heterocycle catalyzedcarbonylation using carbon dioxide may include, but is not limited to,steps (A) to (D). Step (A) may introduce water to a first compartment ofan electrochemical cell. The first compartment may include an anode.Step (B) may introduce carbon dioxide to a second compartment of theelectrochemical cell. The second compartment may include a solution ofan electrolyte, a heterocyclic catalyst, and a cathode. Step (C) mayintroduce at least one of a carboxylic acid, an aldehyde, an alcohol,acetylene, an amine, an aromatic compound, or an epoxide to the secondcompartment of the electrochemical cell. Step (D) may apply anelectrical potential between the anode and the cathode in theelectrochemical cell sufficient to induce liquid phase carbonylation toform a product mixture.

A system may include, but is not limited to, an electrochemical cellincluding a first cell compartment, an anode positioned within the firstcell compartment, a second cell compartment, a separator interposedbetween the first cell compartment and the second cell compartment, anda cathode and a heterocyclic catalyst positioned within the second cellcompartment. The system may also include a carbon dioxide source, wherethe carbon dioxide source may be coupled with the second cellcompartment and may be configured to supply carbon dioxide to thecathode. The system may also include a reactant source coupled with thesecond cell compartment. The reactant source may be configured to supplyat least one of an alkene, a carboxylic acid, an aldehyde, an alcohol,acetylene, an amine, an aromatic compound, or an epoxide to the cathode.The system may also include a fluid source coupled with the first cellcompartment. The system may further include an energy source operablycoupled with the anode and the cathode. The energy source may beconfigured to provide power to the anode and the cathode to induce atleast one of hydroformylation or carbonylation at the cathode and tooxidize the fluid at the anode.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not necessarily restrictive of the disclosure as claimed. Theaccompanying drawings, which are incorporated in and constitute a partof the specification, illustrate an embodiment of the disclosure andtogether with the general description, serve to explain the principlesof the disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The numerous advantages of the present disclosure may be betterunderstood by those skilled in the art by reference to the accompanyingfigures in which:

FIG. 1 is a block diagram of a system in accordance with an embodimentof the present disclosure;

FIG. 2 is a flow diagram of an example method for mitigation of carbondioxide through heterocycle catalyzed hydroformylation using carbondioxide; and

FIG. 3 is a flow diagram of an example method for mitigation of carbondioxide through heterocycle catalyzed carbonylation using carbondioxide.

DETAILED DESCRIPTION

Reference will now be made in detail to the presently preferredembodiments of the present disclosure, examples of which are illustratedin the accompanying drawings.

In accordance with some embodiments of the present disclosure, anelectrochemical system is provided that generally allows carbon dioxideand water to undergo hydroformylation to produce commercially valuableproducts under mild process conditions. In accordance with someembodiments of the present disclosure, an electrochemical system isprovided that generally allows carbon dioxide to participate incarbonylation with another reactant to produce commercially valuableproducts under mild process conditions.

Aldehydes are an important industrial chemical, and are industriallyproduced via hydroformylation using alkenes (olefins) and syngas asreactants. More than nine million metric tons of aldehydes are producedannually using hydroformylation. The alkenes used in hydroformylationmay be produced via catalytic cracking of petroleum. The syngas may beproduced via steam reformation of natural gas.

Other useful industrial chemicals, including organic acids, alcohols,carbonates, and the like, may be industrially produced via carbonylationusing carbon monoxide (e.g., from syngas) and a variety of othermaterials as reactants. Such other materials used as reactants withcarbon monoxide may include acetylene, amines, nitro compounds,aromatics, alcohols, and cyclic molecules. Current carbonylationprocesses include the Monsanto and Cativa Processes for making aceticacid from methanol, Reppe Chemistry, the Koch Reaction, andcarboxylation. Conventional carbonylation processes generally occur athigh pressure and temperature, depending on the desired product.Further, conventional carbonylation processes produce carbon dioxide,thereby further contributing to the concentration of carbon dioxide inthe atmosphere and thus, global climate change.

In some embodiments of the present disclosure, the energy used by thesystems may be generated from an alternative energy source to avoidgeneration of additional carbon dioxide through combustion of fossilfuels. In general, the embodiments for carbon dioxide to participate asa reactant in hydroformylation and carbonylation do not require syngasas reactants. Some embodiments of the present invention thus relate toenvironmentally beneficial methods and systems for reducing carbondioxide, a major greenhouse gas, in the atmosphere thereby leading tothe mitigation of global warming. The embodiments provided herein alsopromote safety by utilizing relatively mild process conditions that donot rely on high pressure/high temperature process conditions. Moreover,certain processes herein are preferred over existing electrochemicalprocesses due to being stable, efficient, having scalable reactionrates, occurring in water, and providing selectivity of desiredproducts.

For electrochemical reductions, the electrode may be a suitableconductive electrode, such as Al, Au, Ag, C, Cd, Co, Cr, Cu, Cu alloys(e.g., brass and bronze), Ga, Hg, In, Mo, Nb, Ni, Ni alloys, Ni—Fealloys, Sn, Sn alloys, Ti, V, W, Zn, stainless steel (SS), austeniticsteel, ferritic steel, duplex steel, martensitic steel, Nichrome,elgiloy (e.g., Co—Ni—Cr), degenerately doped n-Si, degenerately dopedn-Si:As and degenerately doped n-Si:B. Other conductive electrodes maybe implemented to meet the criteria of a particular application. Forphotoelectrochemical reductions, the electrode may be a p-typesemiconductor, such as p-GaAs, p-GaP, p-InN, p-InP, p-CdTe, p-GaInP₂ andp-Si. Other semiconductor electrodes may be implemented to meet thecriteria of a particular application.

Before any embodiments of the invention are explained in detail, it isto be understood that the embodiments may not be limited in applicationper the details of the structure or the function as set forth in thefollowing descriptions or illustrated in the figures of the drawing.Different embodiments may be capable of being practiced or carried outin various ways. Also, it is to be understood that the phraseology andterminology used herein is for the purpose of description and should notbe regarded as limiting. The use of terms such as “including,”“comprising,” or “having” and variations thereof herein are generallymeant to encompass the item listed thereafter and equivalents thereof aswell as additional items. Further, unless otherwise noted, technicalterms may be used according to conventional usage.

A use of electrochemical or photoelectrochemical reactions involvingcarbon dioxide as a reactant, tailored with certain electrocatalysts,may produce commercially valuable chemicals and other products. Thereaction of the carbon dioxide may be suitably achieved efficiently in adivided electrochemical or photoelectrochemical cell in which (i) acompartment contains an anode suitable to oxidize or split the water,and (ii) another compartment contains a working cathode electrode and acatalyst. The compartments may be separated by a porous glass frit,microporous separator, ion exchange membrane, or other ion conductingbridge. Both compartments generally contain an aqueous solution of anelectrolyte. Carbon dioxide gas may be continuously bubbled through thecathodic electrolyte solution to saturate the solution.

Advantageously, the carbon dioxide may be obtained from any source(e.g., an exhaust stream from fossil-fuel burning power or industrialplants, from geothermal or natural gas wells or the atmosphere itself).Most suitably, the carbon dioxide may be obtained from concentratedpoint sources of generation prior to being released into the atmosphere.For example, high concentration carbon dioxide sources may frequentlyaccompany natural gas in amounts of 5% to 50%, exist in flue gases offossil fuel (e.g., coal, natural gas, oil, etc.) burning power plants,and high purity carbon dioxide may be exhausted from cement factories,from fermenters used for industrial fermentation of ethanol, and fromthe manufacture of chemicals and fertilizers. Certain geothermal steamsmay also contain significant amounts of carbon dioxide. The carbondioxide emissions from varied industries, including geothermal wells,may be captured on-site. Separation of the carbon dioxide from suchexhausts is known. Thus, the capture and use of existing atmosphericcarbon dioxide in accordance with some embodiments of the presentinvention generally allow the carbon dioxide to be a renewable andunlimited source of carbon.

Referring to FIG. 1, a block diagram of a system 100 is shown inaccordance with a specific embodiment of the present invention. System100 may be utilized for carbonylation and/or hydroformylation withcarbon dioxide, depending on whether other reactants are introduced withthe carbon dioxide. The system (or apparatus) 100 generally comprises acell (or container) 102, a liquid source 104, a power source 106, a gassource 108, a first extractor 110 and a second extractor 112. A productor product mixture may be presented from the first extractor 110. Anoutput gas may be presented from the second extractor 112.

The cell 102 may be implemented as a divided cell. The divided cell maybe a divided electrochemical cell and/or a divided photochemical cell.The cell 102 is generally operational to process carbon dioxide (CO₂)into products via hydroformylation and/or carbonylation. The reactionmay take place by bubbling carbon dioxide and an aqueous solution of anelectrolyte in the cell 102. A cathode 120 in the cell 102 may inducehydroformylation and/or carbonylation with the carbon dioxide into aproduct mixture that may include one or more compounds. Forhydroformylation processes, the product mixture may include one or morealdehydes. For carbonylation processes, the product mixture may includeone or more organic acids, aldehydes, alcohols, carbonates, and/orcyclic species.

The cell 102 generally comprises two or more compartments (or chambers)114 a-114 b, a separator (or membrane) 116, an anode 118, and a cathode120. The anode 118 may be disposed in a given compartment (e.g., 114 a).The cathode 120 may be disposed in another compartment (e.g., 114 b) onan opposite side of the separator 116 as the anode 118. An aqueoussolution 122 may fill both compartments 114 a-114 b. The aqueoussolution 122 may include water as a solvent and water soluble salts(e.g., potassium chloride (KCl), potassium sulfate (K₂SO₄), or othersuitable salt). A heterocyclic catalyst 124 may be added to thecompartment 114 b containing the cathode 120.

The liquid source 104 may implement a water source. The liquid source104 may be operational to provide pure water to the cell 102.

The power source 106 may implement a variable voltage source. The powersource 106 may be operational to generate an electrical potentialbetween the anode 118 and the cathode 120. The electrical potential maybe a DC voltage.

The gas source 108 may implement a carbon dioxide source. The source 108is generally operational to provide carbon dioxide to the cell 102. Insome embodiments, the carbon dioxide is bubbled directly into thecompartment 114 b containing the cathode 120.

The first extractor 110 may implement an organic product and/orinorganic product extractor. The extractor 110 is generally operationalto extract (separate) one or products of the product mixture from theelectrolyte 122. The extracted products may be presented through a port126 of the system 100 for subsequent storage and/or consumption by otherdevices and/or processes.

The second extractor 112 may implement an oxygen extractor. The secondextractor 112 is generally operational to extract oxygen (e.g., O₂)byproducts created by the reduction of the carbon dioxide and/or theoxidation of water. The extracted oxygen may be presented through a port128 of the system 100 for subsequent storage and/or consumption by otherdevices and/or processes. Chlorine and/or oxidatively evolved chemicalsmay also be byproducts in some configurations, such as in an embodimentof processes other than oxygen evolution occurring at the anode 118.Such processes may include chlorine evolution, oxidation of organics,and corrosion of a sacrificial anode. Any other excess gases (e.g.,hydrogen) created by the reduction of the carbon dioxide and water maybe vented from the cell 102 via a port 130.

In the hydroformylation and/or carbonylation processes, water may beoxidized (or split) to protons and oxygen at the anode 118 while thecarbon dioxide is reduced to the product mixture at the cathode 120. Theelectrolyte 122 in the cell 102 may use water as a solvent with anysalts that are water soluble, including potassium chloride (KCl) andpotassium sulfate (K₂SO₄) and with a suitable heterocyclic catalyst 124,such as imidazole, pyridine, or any substituted variant with one or more5- or 6-member heterocyclic ring. In general, at least 1% water of atotal amount of liquid in the cathode compartment solution should bepresent in order to provide sufficient protons for the desired reaction(e.g., hydroformylation and/or carbonylation) to occur. Cathodematerials generally include any conductor. However, efficiency of theprocess may be selectively increased by employing a catalyst/cathodecombination selective for a hydroformylation and/or carbonylation withcarbon dioxide to a product mixture. For catalytic reduction of carbondioxide, the cathode materials may include Sn, Ag, Cu, Rh, Fe, Co, In,steel (e.g., 316 stainless steel), and alloys of Co, Cu, and Ni. Thematerials may be in bulk form. Additionally and/or alternatively, thematerials may be present as particles or nanoparticles loaded onto asubstrate, such as graphite, carbon fiber, or other conductor.

An anode material sufficient to oxidize or split water may be used. Theoverall process may be generally driven by the power source 106.Combinations of cathodes 120, electrolytes 122, and heterocycliccatalysts 124 may be used to control the reaction products of the cell102.

For hydroformylation processes, carbon dioxide is introduced to thecathode 120 in the compartment 114 b. For instance, carbon dioxide maybe bubbled into the compartment 114 b. An alkene is also introduced tothe compartment 114 b, such as from a reactant source. The alkene mayinclude, for example, ethylene, propylene, 1-butylene, 2-butylene,butadiene, 3-buten-1-ol, an allyl alcohol, an unsaturated alcohol, or anunsaturated organic reactant. A metallic or non-metallic cathode in thecompartment 114 b may be sustained at an electric potential of betweenapproximately −0.5 and −2V vs. SCE (saturated calomel electrode) inorder to drive the hydroformylation with the aid of the heterocycliccatalyst 124. The reaction may occur at mild process conditions, forexample, at ambient temperature and pressure.

The reaction process for hydroformylation in the electrochemical cell102 may involve the heterocyclic catalyst 124, available protons, andthe cathode 120 interacting to form a radical, as described in U.S.patent application Ser. No. 12/696,840, entitled “Conversion of CarbonDioxide to Organic Products,” which is hereby incorporated by reference.The radical formed by the interaction of the heterocyclic catalyst 124,available protons, and the cathode 120 may react with carbon dioxide toproduce a hydroxy formyl radical. The carbon dioxide is thus activatedand available to react with the alkene present in the compartment 114 b.The formyl radical and the alkene may react in a manner analogous tohydroformylation to produce a product mixture. The product mixture mayinclude one or more of a carboxylic acid, an aldehyde, or an alcohol,depending on the cathode material, the heterocyclic catalyst 124, andthe reaction conditions of the cell 102. In other embodiments, theproduct mixture may include one or more of a hydroxy aldehyde, a hydroxycarboxylic acid, or a diol if an allyl alcohol or 3-buten-1-ol is usedas the alkene reactant. Metal oxide catalysts may be added to thecompartment 114 b to accelerate the reaction and/or to improveselectivity of a desired product.

For carbonylation processes, carbon dioxide is introduced to the cathode120 in the compartment 114 b. For instance, carbon dioxide may bebubbled into the compartment 114 b. A second reactant is also introducedto the compartment 114 b, such as from a reactant source. The secondreactant may include, for example, a carboxylic acid, an aldehyde, analcohol, acetylene, an amine, an aromatic compound, or an epoxide. Ametallic or non-metallic cathode in the compartment 114 b may besustained at an electric potential of between approximately −0.5 and −2Vvs. SCE (saturated calomel electrode) in order to drive thecarbonylation with the aid of the heterocyclic catalyst 124. Thereaction may occur at mild process conditions, for example, at ambienttemperature and pressure.

The reaction process for carbonylation in the electrochemical cell 102may involve two pathways. In the first, the heterocyclic catalyst 124,available protons, and the cathode 120 interacting to form a radical, asdescribed in U.S. patent application Ser. No. 12/696,840, entitled“Conversion of Carbon Dioxide to Organic Products,” which isincorporated by reference. The radical formed by the interaction of theheterocyclic catalyst 124, available protons, and the cathode 120 mayreact with carbon dioxide to produce a hydroxy formyl radical. Thecarbon dioxide is thus activated and available to react with the secondreactant present in the compartment 114 b. The formyl radical and thesecond reactant may react in a manner analogous to carbonylation toproduce a product mixture.

In the second pathway, the carbon dioxide in compartment 114 b may bereduced to carbon monoxide (CO) at the cathode 120. The carbon monoxidemay react with the second reactant present in the compartment 114 b toform the carbonylation product mixture. The product mixture under eitherpathway may include one or more organic acid, aldehyde, alcohol,carbonate, cyclic compound, or a combination thereof. Metal oxidecatalysts may be added to the compartment 114 b to accelerate thereaction and/or to improve selectivity of a desired product.

As described herein, the present disclosure may be implemented via anelectrochemical cell wherein carbon dioxide and another reactant isprocessed to form a product mixture. For hydroformylation, the otherreactant may include an alkene. For carbonylation, the other reactantmay include, for example, a carboxylic acid, an aldehyde, an alcohol,acetylene, an amine, an aromatic compound, or an epoxide. Forhydroformylation and for carbonylation, additional metal oxide or metalreaction promoters may be added to the catholyte to improve the kineticsand/or selectivity of the process.

Referring to FIG. 2, a flow diagram of an example method 200 forhydroformylation with carbon dioxide is shown. The method (or process)200 generally comprises a step (or block) 202, a step (or block) 204, astep (or block) 206, and a step (or block) 208. The method 200 may beimplemented using the system 100.

In the step 202, water may be introduced to a first compartment of anelectrochemical cell. The first compartment may include an anode.Introducing carbon dioxide to a second compartment of theelectrochemical cell may be performed in the step 204. The secondcompartment may include a solution of an electrolyte, a heterocycliccatalyst, and a cathode. In the step 206, an alkene may be introduced tothe second compartment of the electrochemical cell. In the step 208, anelectric potential may be applied between the anode and the cathode inthe electrochemical cell sufficient for the cathode to induce liquidphase hydroformylation to form a product mixture.

Referring to FIG. 3, a flow diagram of an example method 300 forcarbonylation with carbon dioxide is shown. The method (or process) 300generally comprises a step (or block) 302, a step (or block) 304, a step(or block) 306, and a step (or block) 308. The method 300 may beimplemented using the system 100.

In the step 302, water may be introduced to a first compartment of anelectrochemical cell. The first compartment may include an anode.Introducing carbon dioxide to a second compartment of theelectrochemical cell may be performed in the step 304. The secondcompartment may include a solution of an electrolyte, a heterocycliccatalyst, and a cathode. In the step 306, at least one of a carboxylicacid, an aldehyde, an alcohol, acetylene, an amine, an aromaticcompound, or an epoxide may be introduced to the second compartment ofthe electrochemical cell. In the step 308, an electric potential may beapplied between the anode and the cathode in the electrochemical cellsufficient for the cathode to induce liquid phase carbonylation to forma product mixture.

EXAMPLE 1 Hydroformylation

The hydroformylation of allyl alcohol with carbon dioxide was performedelectrochemically using pyridine as a homogenous catalyst. The projectwas aimed at the carbon-carbon coupling of pyridine catalyzedformyl/carboxyl/carbamate to the surface bound alkene group of thereactant. The reaction was conducted with a cobalt cathode. The cathodewas held at −1V vs SCE using a potentiostat. 0.5M potassium chloride wasused as the electrolyte, with water as the solvent for the reaction.Allyl alcohol was in solution in the cathode compartment and carbondioxide was bubbled through the solution during electrolysis. The anodecompartment also contained water with potassium sulfate electrolyte anda water oxidation anode manufactured by De Nora. In the case of cobaltcathodes, aldehyde product indicative of hydroformylation of the allylalcohol was observed using 1H NMR analysis.

EXAMPLE 2 Hydroformylation

In another investigation, similar reaction was performed with a cobaltcathode using 3-buten-1-ol instead of the allyl alcohol. As similar toallyl alcohol studies an aldehyde product was observed using 1H NMR.

EXAMPLE 3 Carbonylation

Carbonylation of glyoxal was conducted with carbon dioxide in anelectrochemical reactor. The cathode material was indium. The anode wasa water oxidation anode manufactured by De Nora. The catholyte consistedof 0.5M potassium chloride and pyridine heterocycle catalyst in waterwith glyoxal in solution and carbon dioxide bubbled through the cathodecompartment. The anolyte consisted of 0.5M potassium sulfate in water.The cathode was held at −1.46V vs SCE using a potentiostat. Three carbonproducts, to include propanal and acetone were observed using 1H NMR,demonstrating the reductive carbonylation of glyoxal with carbondioxide.

It is believed that the present disclosure and many of its attendantadvantages will be understood by the foregoing description, and it willbe apparent that various changes may be made in the form, constructionand arrangement of the components thereof without departing from thescope and spirit of the disclosure or without sacrificing all of itsmaterial advantages. The form herein before described being merely anexplanatory embodiment thereof, it is the intention of the followingclaims to encompass and include such changes.

What is claimed is:
 1. A method for hydroformylation with carbondioxide, comprising: (A) introducing water to a first compartment of anelectrochemical cell, said first compartment including an anode; (B)introducing carbon dioxide to a second compartment of saidelectrochemical cell, said second compartment including a solution of anelectrolyte, a heterocyclic catalyst, and a cathode; (C) introducing analkene to said second compartment of said electrochemical cell; and (D)applying an electrical potential between said anode and said cathode insaid electrochemical cell sufficient for said cathode to induce liquidphase hydroformylation to form a product mixture.
 2. The method of claim1, wherein said product mixture includes at least one of a carboxylicacid, an aldehyde, or an alcohol.
 3. The method of claim 1, wherein saidsolution of said electrolyte includes at least one of potassium chlorideor potassium sulfate.
 4. The method of claim 1, where said heterocycliccatalyst includes at least one of imidazole, pyridine, or a substitutedvariant of imidazole or pyridine, said substituted variant including atleast one of a five member heterocyclic ring or a six memberheterocyclic ring.
 5. The method of claim 1, wherein said secondcompartment further includes a metal oxide reaction promoter.
 6. Themethod of claim 1, wherein said alkene includes at least one ofethylene, propylene, 1-butylene, 2-butylene, butadiene, an unsaturatedalcohol, or an unsaturated organic reactant.
 7. The method of claim 1,wherein applying an electrical potential between said anode and saidcathode in said electrochemical cell includes: applying a potential ofbetween approximately −0.5 and −2V vs. SCE (saturated calomel electrode)at said cathode.
 8. The method of claim 1, wherein applying anelectrical potential between said anode and said cathode in saidelectrochemical cell includes: applying an electrical potential betweensaid anode and said cathode in said electrochemical cell at ambienttemperature and pressure.
 9. The method of claim 1, wherein said secondcompartment further includes at least one percent water of a totalamount of liquid in said second compartment.